CN105131318A - Method of regulating surface wettability of parylene c by virtue of surface patterning - Google Patents
Method of regulating surface wettability of parylene c by virtue of surface patterning Download PDFInfo
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Abstract
The invention discloses a method of regulating the surface wettability of a parylene c (PC) by virtue of surface patterning. The method comprises the following steps: ultrasonically washing the PC, and then drying the PC for standby application; processing the PC by virtue of air plasma for standby application; then smearing a polymer coating rich in polarity groups such as hydroxyl, carboxyl, amino group and the like on the surface of the PC, and drying; placing a patterned mask above the processed PC, and then carrying out a cross-linking reaction under the effect of UV/O3; after the cross-linking is completed, soaking in deionized water to wash out unreacted and ungrafted polymer coating rich in the polarity groups, and then drying to obtain a patterned PC with controllable surface wettability. According to the method of regulating the surface wettability of the PC by virtue of the surface patterning, the wettability is adjustable, a surface water contact angle can be regulated and designed in a range of 5 to 90 degrees, so that the surface wettability of the PC can be precisely designed according to the real requirement of different fields, and the yield of products is increased.
Description
Technical field
The present invention relates to macromolecule material surface modification, particularly a kind of method by patterned surface accuracy controlling Parylene C film surface wettability, belong to surface wettability regulation and control field.
Background technology
Parylene C film (PlaryleneC film, be called for short PC film) due to film-forming process relative maturity, and there is lower gas and vapor permeability, excellent dielectric properties, solvent resistance and mechanical property, be considered to the most effective moisture proof at present, mould proof, one of Defend salt fog and high-frequency unit barrier material, in aerospace, Military Electronics, microelectronics, semi-conductor, biologic medical, the fields such as historical relic's protection have a wide range of applications (PurselS, HornMW, DemirelMC, LakhtakiaA.Growthofsculpturedpolymersubmicronwireassembl iesbyvapordeposition.Polymer.2005, 46 (23): 9544-9548).
But in its preparation process, by the impact of deposition parameter and other factors, easily there is the defect problems such as degree of crystallinity is low, local damage in PC film, this makes the actual vapor obstructing capacity decline (Chen Yanping of resulting materials, handsome luxuriant soldier, fresh dawn is refined, lucky ripple, the deposition polymerization process of Tang Xian minister .Parylene film and influence factor thereof. material Leader .2007 (S3); WeiL, ParhiP, VoglerEA, RittyTM, LakhtakiaA.Thickness-controlledhydrophobicityoffibrousPa rylene-Cfilms.MaterialsLetters.2010; 64 (9): 1063-1065).
By to PC membrane surface modification, at the fine and close barrier layer of the surface structure of film, not affecting body construction and the character of film, is the conventional approach improving PC film water vapour locking separating performance before an entry.Inorganic coating is the preferred material strengthening water vapor rejection, wherein, Al, Al2O3, SiO2, SiOx, SiOxNy, AlOxNy etc. apply more inorganic coating (LiangX, KingDM, GronerMD, BlacksonJH, HarrisJD, GeorgeSM, etal.Barrierpropertiesofpolymer/aluminananocompositememb ranesfabricatedbyatomiclayerdeposition.JournalofMembrane Science.2008; 322 (1): 105-112; ChartonC, SchillerN, FahlandM,
a, WedelA, NollerK.Developmentofhighbarrierfilmsonflexiblepolymersu bstrates.ThinSolidFilms.2006; 502 (1-2): 99-103; Amberg-SchwabS, HoffmannM, BaderH, GesslerM.Inorganic-OrganicPolymerswithBarrierPropertiesf orWaterVapor, OxygenandFlavors.JournalofSol-GelScienceandTechnology.19 98; 13 (1-3): 141-146).
But because the surface energy of PC film is very low, anergy functional group, cause inorganic coating poor in the bonding force on PC film surface, coating easily peels off inefficacy.Therefore, need the surface energy improving PC film further, realize the Effective Regulation to its surface wettability.
At present mainly contain two kinds to the means that polymkeric substance carries out surface wettability regulation and control, one is the chemical modification by surface, changes the chemical polarity of surface of polymer material, thus realizes its wettability modification; Two is by constructing coarse physical structure at polymer surfaces, utilizes surfaceness to change its surface wettability.Mainly introduce by selective wet chemical etching modification the surface wettability that sulfonic acid isopolarity group improves PC film, but this method easily causes PC erosion degrade, the shortcomings such as also dangerous, operation is inconvenient of the use of strong acid simultaneously.Plasma surface modification process PC film is relatively gentle dry method treatment technology, oxygen gas plasma can be utilized to increase the content of the polar functional group (as carbonyl, hydroxyl etc.) of polymer film surface, thus improve the surface wettability of polymeric film, but the main drawback of this method is energy of plasma, and the uncontrollable film degradation that may cause is destroyed, phenomenon of the more important thing is that oxygen-containing functional group there will be in time " disappearing ", the surface wetting capability of polymeric film is made to reduce (AppliedSurfaceScience, 2012,261:43 – 51).In addition, by this method, chemical modification is carried out to PC film, also there is surface wettability and be difficult to accurately adjustable deficiency.And although the method passing through to introduce on PC film surface physical aspects can change its surface wettability, but because PC film is the hydrophobic surface of low surface energy, thus the introducing of roughness can improve the hydrophobic ability on its surface further, and cannot meet the demand that its surface energy of raising reduces hydrophobic ability.Therefore, need new technique means to realize the accuracy controlling to PC film surface wettability, prepare high surface energy and can the hydrophilic PC film existed steady in a long-term.
Patterned surface has compound with regular structure, and designability is comparatively strong, thus obtains and pays close attention to widely.For the preparation of pattern structure, method conventional at present comprises: (1) reactive ion etching (ParkSG, MoonHH, LeeSK, ShimJ, YangSM.BioinspiredHolographicallyFeaturedSuperhydrophobi candSuperstickyNanostructuredMaterials.Langmuir.2010; 26 (3): 1468-1472); (2) Soft lithograph (LiX, WangTQ, ZhangJH, YanX, ZhangXM, ZhuDF, etal.ModulatingTwo-DimensionalNon-Close-PackedColloidalC rystalArraysbyDeformableSoftLithography.Langmuir.2010; 26 (4): 2930-2936); (3) self-assembly (JungYS, ChangJB, VerploegenE, BerggrenKK, RossCA.APathtoUltranarrowPatternsUsingSelf-AssembledLith ography.NanoLetters.2010; 10 (3): 1000-1005); (4) photo-irradiation treatment (JungYS, ChangJB, VerploegenE, BerggrenKK, RossCA.APathtoUltranarrowPatternsUsingSelf-AssembledLith ography.NanoLetters.2010 under mask effect; 10 (3): 1000-1005) etc.
Wherein, structural form prepared by mask photo-irradiation treatment is easily controlled, and easily carries out large-area treatment, and mask can Reusability, and cost is lower, and mask can design according to ideal structure, is beneficial to the continuous regulation and control realized PC film surface wettability.But directly photo-irradiation treatment may cause PC film superficial degradation, thus affects its original transparency, water vapor rejection performance etc.Therefore, need to adopt new approaches to process PC film, to meet accurately adjustable, the wettability existence steady in a long-term of its surface wettability, not affect the object of its original excellent properties.
Summary of the invention
The object of the invention is to overcome in prior art in order to strengthen PC film surface water vapour locking separating performance improve PC film surface wetting capability time, illumination existing for mask photo-irradiation treatment causes the problem of PC film superficial degradation, provides a kind of method by patterned surface regulation and control PC film surface wettability.The method can overcome in During Illumination the defect causing degrading, and makes PC film in surperficial masking steps, keep satisfactory stability and degradation problem does not occur.
Another object of the present invention is to provide a kind of surface wettability continuously adjustabe, wettability long-term stability can exist and not lose the PC film of original excellent properties.
For achieving the above object, the invention provides following technical scheme:
By a method for patterned surface regulation and control Parylene C film surface wettability, comprise the following steps:
(1) Parylene C film, ultrasonic cleaning, dry.
(2) by the pre-treatment of above-mentioned Parylene C film air plasma.
(3) then, the polymeric coating of polar group is contained in Parylene C film surface-coated, dry.
(4) mask (being called for short: the mask of patterning) with patterning hole is placed in above Parylene C film, then at UV/O
3crosslinking reaction is carried out under (ultraviolet/ozone) effect.
(5) finally by the Parylene C film after crosslinked, the polymeric coating of wash-out removing unreacted grafting is soaked in deionized water, dry, obtain the film that patterning is modified.This film is the improved Parylene C film of surface wettability, and have wetting ability good, water droplet contact angle is little, and the feature that surface wettability is controlled.
The mask of the patterning used in the present invention is the mask with certain figure hole, it can make some light be radiated on PC membrane sample by the hole on it while covering PC membrane sample, and then realize the regulation and control of the quantity of illumination, reach the tuned into the melt process of illumination cross-link intensity.The shape of hole can adjust arbitrarily according to actual needs, reaches the object of control ultraviolet/ozone intensity.
Further scheme is, in step (1), Parylene C film carries out ultrasonic cleaning in acetone and/or ethanol.During ultrasonic cleaning, film is subject to the acoustic wave action in all directions in a liquid, and solution easily produces cavitation, acceleration and direct flow effect under ultrasonication, make the dirt of film surface directly be washed away stripping by solution, make that crud layer is disperseed, emulsification, stripping and reach cleaning object.Ultrasonic have easy to clean, the feature that cleaning performance is good, and the cleanup action for Parylene C film is very outstanding, can provide good basic guarantee for follow-up air plasma process.
Further scheme is, described in step (2), air plasma preconditioned voltage is 50 ~ 200V, and the treatment time is 1 ~ 60s.Air plasma is isoionic state gas exerts energy being made it to ionization formation, when utilizing air plasma to carry out pretreated to film, plasma body only reacts at film surface, and the treatment time is very short, material internal is substantially unaffected, film sample surface adhesion performance through Cement Composite Treated by Plasma improves greatly, tentatively can adhere to the polymkeric substance containing polar group, is conducive to the effect promoting that follow-up illumination is crosslinked.
Further scheme is, the polymkeric substance containing polar group described in step (3) refers to the polymkeric substance being rich in hydroxyl, carboxyl, amino groups.Coating polymeric materials containing polar group, on PC film surface, because PC film is through air plasma process, so hydrophilic polar group polymkeric substance is attached to its surface fast, tentatively obtains the PC membrane sample that wettability is good.
Further scheme is, the described polar group polymkeric substance contained is one or more in polyacrylic acid (PAA), polyoxyethylene (PEO), Natvosol (HEC), chitosan quaternary ammonium salt (HTCC), polyacrylamide (PAM).All containing a large amount of polar hydrophilic groups in the molecule of the polymer materialss such as PAA, PEO, HEC, HTCC, PAM, when it is coated in PC film surface, first electrostatic adhesion is formed by the PC film surface of polar group and Cement Composite Treated by Plasma, then be cross-linked by illumination and realize reliable and stable chemical bond connection, finally reach the object improving PC film wettability of the surface.
Further scheme is, the polymkeric substance of the described polar group contained is coated on Parylene C film surface with the solution form that mass concentration is 0.01 ~ 5%, and the solvent of solution is the one or both mixture in water, ethanol.Polar group polymkeric substance has good wetting ability, it is directly dissolved in the solution of water and/or ethanol and both can reaches homodisperse effect, can improve again and well control its consumption in coating procedure, ensure that the polymer modification material being rich in polar group forms thin and uniform coating on PC film surface, and then make PC film various piece in illumination cross-linking process all can form good coating sample uniformly.
Further scheme is, in step (3), coating method comprises the one in dip-coating, spin coating, spraying, brushing, roller coating.Coating method has multiple, and adopt suitable coating method can better tackle in the different conditions of production, particularly some coated weights are larger, the situation that uniformity requirement is high, adopts roller coating to be good selection.The mode of dip-coating, spraying etc. then can be considered when coated sample out-of-shape.
Further scheme is, the hole of mask described in step (4) is the one in circular hole, tri-angle-holed, square hole, hexagonal hole, and hole area accounts for 5 ~ 50% of mask area, and hole between centers is 10 ~ 1000 μm.The present invention, in order to control the area accounting of the surface-crosslinked hydrophilic polymer article pattern of PC film well, have selected the mask plate that hole area accounts for mask area 5% ~ 50%.The mask of ratio like this can ensure UV/O
3time illumination is cross-linked, the light intensity covered is appropriate, and during accounting lower than 5%, the hydrophilic polymer component amount on crosslinked very little, or easily peel off by cross-link intensity deficiency, and then it is less to make surface wettability reduce amplitude.When hole area accounting is greater than 50%, crosslinked excessive in conjunction with the amount of hydrophilic polymer, PC film surface properties changes comparatively large, may be unfavorable for promoting its water vapor rejection performance.
Further scheme is, UV/O described in step (4)
3treatment time is 10 ~ 600 seconds (s).UV/O
3illumination pretreatment process is that the crosslinked initiation of the hydrophilic layer of PC film surface coating is crucial, because the effect of surface modification is just played in coating, so its gauge control is thinner, and then UV/O
3the time of photo-irradiation treatment can control very short.Treatment time controls within 10 ~ 600 seconds, and PC membrane surface modification effect both can have been made to reach desired value, the destruction of ultraviolet for the substrate of PC film can be controlled in minimum degree again.So, UV/O in step 4
3the pretreated time is 10 ~ 600 seconds.
Further scheme is, soaking elution time in deionized water described in step (5) is 10 ~ 60min.Soak mainly wash-out in deionized water by the uncrosslinked hydrophilic polymer composition of mask shield portions, soak time controls according to the quantity of the hydrophilic composition treating wash-out, the hydrophilic component that abundant wash-out is uncrosslinked should be ensured, prevent deionized water from being destroyed by the hydrophilic composition be just cross-linked again.By a large amount of experimental studies, contriver finds that the best results of wash-out, the PC film after wash-out process tests the water contact angle that obtains closest to actual service condition when adopting the time controling of deionized water immersion wash-out within 10 ~ 60 minutes.
Further scheme is, described in step (5), drying treatment temperature is 30 ~ 90 DEG C, and the time is 20 ~ 120min.The PC film of crosslinked upper hydrophilic polymer layer is due to problem of solidification, initial stage use temperature should not be too high, the temperature controlling drying treatment process is no more than 90 DEG C, can effectively reduce the ratio of the structural failure of film surface, and then improves the work-ing life of film and successive modified potentiality.
Further scheme is, the film surface water contact angle scope that patterning described in step (5) is modified is 5 ~ 90 °.Patterning modification technique makes film surface water contact angle can adjust control arbitrarily, adjusts different water contact angles for different situations, to adapt to practical situations better.
Compared with prior art, beneficial effect of the present invention:
Method by patterned surface regulation and control PC film surface wettability of the present invention, there is wettability adjustable, surface water contact angle can carry out regulation and control design between 5 ~ 90 °, thus the careful design of PC film surface wettability can be carried out according to the actual demand of different field, improve the good article rate of product.
In addition, the PC film surface wettability obtained has long stability, can maintain more than 1 month under natural laying state.
In addition, the method of the invention can realize only selecting wherein suitable a kind of polymeric coating being rich in polar group for different field, get final product Effective Regulation wettability of the surface, avoid the shortcoming that traditional different surfaces wettability design needs different types of polymeric coating.
Meanwhile, the method for the invention is the hydrophilic polymer coating preparing patterning on PC film surface, avoids the performance destruction that conventional surface wettability treatment process may produce PC film.
Accompanying drawing illustrates:
Fig. 1 is the optical photograph (hole area is 50%) of the embodiment of the present invention 5 circular hole mask used.
Fig. 2 is the structural representation (vertical view) of the patterning PC film that the mask used version of the present invention prepares.
Fig. 3 is the structural representation (side-view) of the patterning PC film that the mask used version of the present invention prepares.
Fig. 4 is the water droplet contact angle sectional view of comparative example 1 ~ 3 sample surfaces of the present invention.
Fig. 5 is the water droplet contact angle sectional view of the embodiment of the present invention 1 ~ 5 sample surfaces.
Mark in figure: 1-wetting ability pattern, the substrate of 2-PC film.
Embodiment
Below in conjunction with test example and embodiment, the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention is only limitted to following embodiment, all technology realized based on content of the present invention all belong to scope of the present invention.
Comparative example 1
PC film through acetone, EtOH Sonicate cleaning 10min after 50 DEG C of dry 90min, after without any process, test its surperficial water droplet contact angle and transparency.
Comparative example 2
PC film is 50 DEG C of dry 90min after acetone, EtOH Sonicate cleaning 10min, rear directly through UV/O
3process 300s after washing 30min, then 50 DEG C of dry 90min, test its surperficial water droplet contact angle and transparency.
Comparative example 3
PC film is 50 DEG C of dry 90min after acetone, EtOH Sonicate cleaning 10min, by air plasma 100V pre-treatment 10s, and 50 DEG C of dry 90min after the PAA aqueous solution of then 3000rpm, 30s spin coating 1wt%, rear directly through UV/O
3process 300s after washing 30min, then 50 DEG C of dry 90min, test its surperficial water droplet contact angle and transparency.
Embodiment 1
PC film is 50 DEG C of dry 90min after acetone, EtOH Sonicate cleaning 10min, by air plasma 100V pre-treatment 10s, 50 DEG C of dry 90min after the PAA aqueous solution of then 3000rpm, 30s spin coating 1wt%, then be 10% by hole area, hole between centers is that the circular hole mask of 280 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 300s after washing 30min, then 50 DEG C of dry 90min, test its surperficial water droplet contact angle and transparency.
The structure of patterning PC film is as shown in Fig. 2 (vertical view), Fig. 3 (side-view).Under the effect of covering of the pertusate mask of surperficial tool, PC film surface after illumination is cross-linked has a large amount of wetting ability pattern (preferably equally distributed, Fig. 2 is equally distributed example), these wetting ability patterns have remarkable effect for the water droplet contact angle improving PC film surface.
Depict multiple different pattern form in note 1: Fig. 2, certain those skilled in the art can also adopt other pattern suitable arbitrarily to realize identical object.
Note 2: although Fig. 2 and Fig. 3 is vertical view and side-view, the view of the same sample that both are not supporting.Because Fig. 2 is in order to represent multiple different pattern form, and Fig. 3 mainly embodies pattern in side-view is the hydrophilic layer structure being attached to PC film surface.
Embodiment 2
PC film is 50 DEG C of dry 90min after acetone, EtOH Sonicate cleaning 10min, by air plasma 100V pre-treatment 10s, 50 DEG C of dry 90min after the PAA aqueous solution of then 3000rpm, 30s spin coating 1wt%, then be 20% by hole area, hole between centers is that the circular hole mask of 198 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 300s after washing 30min, then 50 DEG C of dry 90min, test its surperficial water droplet contact angle and transparency.
Embodiment 3
PC film is 50 DEG C of dry 90min after acetone, EtOH Sonicate cleaning 10min, by air plasma 100V pre-treatment 10s, 50 DEG C of dry 90min after the PAA aqueous solution of then 3000rpm, 30s spin coating 1wt%, then be 30% by hole area, hole between centers is that the circular hole mask of 162 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 300s after washing 30min, then 50 DEG C of dry 90min, test its surperficial water droplet contact angle and transparency.
Embodiment 4
PC film is 50 DEG C of dry 90min after acetone, EtOH Sonicate cleaning 10min, by air plasma 100V pre-treatment 10s, 50 DEG C of dry 90min after the PAA aqueous solution of then 3000rpm, 30s spin coating 1wt%, then be 40% by hole area, hole between centers is that the circular hole mask of 140 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 300s after washing 30min, then 50 DEG C of dry 90min, test its surperficial water droplet contact angle and transparency.
Embodiment 5
PC film is 50 DEG C of dry 90min after acetone, EtOH Sonicate cleaning 10min, by air plasma 100V pre-treatment 10s, 50 DEG C of dry 90min after the PAA aqueous solution of then 3000rpm, 30s spin coating 1wt%, then be 50% by hole area, hole between centers is the circular hole mask of 125 μm, the optical photograph of mask as shown in Figure 1, is placed in above above-mentioned PC film, rear directly through UV/O
3process 300s after washing 30min, then 50 DEG C of dry 90min, test its surperficial water droplet contact angle and transparency.
Embodiment 6
PC film is 30 DEG C of dry 120min after acetone, EtOH Sonicate cleaning 10min, by air plasma 50V pre-treatment 60s, 30 DEG C of dry 120min after the PAA aqueous solution of then 3000rpm, 30s spin coating 0.5wt%, then be 30% by hole area, hole between centers is that the circular hole mask of 50 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 480s after washing 15min, then 30 DEG C of dry 120min, test its surperficial water droplet contact angle and transparency.
Embodiment 7
PC film is 60 DEG C of dry 60min after acetone, EtOH Sonicate cleaning 10min, by air plasma 150V pre-treatment 45s, 60 DEG C of dry 60min after the PAA ethanolic soln of then 10s dip-coating 0.1wt%, then be 30% by hole area, hole between centers is that the tri-angle-holed mask of 350 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 150s after washing 60min, then 60 DEG C of dry 60min, test its surperficial water droplet contact angle and transparency.
Embodiment 8
PC film is 30 DEG C of dry 120min after acetone, EtOH Sonicate cleaning 10min, by air plasma 50V pre-treatment 60s, 30 DEG C of dry 120min after the PEO aqueous solution of then 3000rpm, 30s spin coating 0.5wt%, then be 30% by hole area, hole between centers is that the square hole mask of 500 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 480s after washing 15min, then 30 DEG C of dry 120min, test its surperficial water droplet contact angle and transparency.
Embodiment 9
PC film is 90 DEG C of dry 30min after acetone, EtOH Sonicate cleaning 10min, by air plasma 200V pre-treatment 3s, then 5s spray 2wt% the PEO aqueous solution after 90 DEG C of dry 30min, then be 10% by hole area, hole between centers is that the hexagonal hole mask of 750 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 90s after washing 60min, then 90 DEG C of dry 30min, test its surperficial water droplet contact angle and transparency.
Embodiment 10
PC film is 30 DEG C of dry 120min after acetone, EtOH Sonicate cleaning 10min, by air plasma 50V pre-treatment 60s, 30 DEG C of dry 120min after the HEC aqueous solution of then 3000rpm, 30s spin coating 0.5wt%, then be 30% by hole area, hole between centers is that the tri-angle-holed mask of 950 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 480s after washing 15min, then 30 DEG C of dry 120min, test its surperficial water droplet contact angle and transparency.
Embodiment 11
PC film is 50 DEG C of dry 90min after acetone, EtOH Sonicate cleaning 10min, by air plasma 50V pre-treatment 45s, then 10s brush 3wt% the HEC aqueous solution after 50 DEG C of dry 90min, then be 20% by hole area, hole between centers is that the square hole mask of 500 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 30s after washing 60min, then 50 DEG C of dry 90min, test its surperficial water droplet contact angle and transparency.
Embodiment 12
PC film is 30 DEG C of dry 120min after acetone, EtOH Sonicate cleaning 10min, by air plasma 50V pre-treatment 60s, 30 DEG C of dry 120min after the HTCC aqueous solution of then 3000rpm, 30s spin coating 0.5wt%, then be 30% by hole area, hole between centers is that the hexagonal hole mask of 300 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 480s after washing 15min, then 30 DEG C of dry 120min, test its surperficial water droplet contact angle and transparency.
Embodiment 13
PC film is 80 DEG C of dry 60min after acetone, EtOH Sonicate cleaning 10min, by air plasma 100V pre-treatment 30s, 80 DEG C of dry 60min after the HTCC ethanolic soln of then 10s roller coating 4wt%, then be 20% by hole area, hole between centers is that the tri-angle-holed mask of 150 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 240s after washing 60min, then 80 DEG C of dry 60min, test its surperficial water droplet contact angle and transparency.
Embodiment 14
PC film is 80 DEG C of dry 60min after acetone, EtOH Sonicate cleaning 10min, by air plasma 150V pre-treatment 30s, 80 DEG C of dry 60min after the PAM aqueous solution of then 10s dip-coating 2wt%, then be 40% by hole area, hole between centers is that the square hole mask of 100 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 360s after washing 30min, then 80 DEG C of dry 60min, test its surperficial water droplet contact angle and transparency.
Embodiment 15
PC film is 80 DEG C of dry 60min after acetone, EtOH Sonicate cleaning 10min, by air plasma 200V pre-treatment 15s, then 10s spray 5wt% the PAM aqueous solution after 80 DEG C of dry 60min, then be 50% by hole area, hole between centers is that the hexagonal hole mask of 210 μm is placed in above above-mentioned PC film, rear directly through UV/O
3process 600s after washing 60min, then 80 DEG C of dry 60min, test its surperficial water droplet contact angle and transparency.
Performance evaluation
In order to test surface wettability and the stability thereof of sample, contact angle result of variations is as shown in table 1 below, and the transparency of sample is with the transmitance of 550nm wavelength for reference in addition, and result is as following table.
Table 1 embodiment primary variables parameter and sample surfaces contact angle test result
As seen from the above table, when adopting method of the present invention to carry out modification to PC film wettability of the surface, can adjust as required and control mask hole area accounting, and then realize the accounting of wetting ability pattern on PC film surface, the water contact angle of film is is freely regulated and controled in the scope of 5 ~ 90 °.
As shown in Figure 4, wherein (a) ~ (c) is corresponding in turn to the PC membrane sample of comparative example 1 ~ 3 to the water droplet contact angle sectional view test result of comparative example 1 ~ 3 sample surfaces.The surface contact angle of visible original PC film (comparative example 1) is comparatively large, changes not obvious in time, but cannot meet the demand to its low contact angle in practical application; When not adopting mask controlled light intensity, when directly carrying out surface-treated sample (comparative example 2), though contact angle has obvious reduction than original PC film, but its less stable, after one month, namely water droplet contact angle has and significantly recovers, and cannot realize the stable regulation and control of PC film wettability, the sample surfaces of comparative example 2 exists certain xanthochromia in addition, its transparency also has obvious reduction, thus the actual use of impact; For the sample (comparative example 3) by containing PAA coating after air plasma process, its surface contact angle has more obvious decline than comparative example 2, and its stability is also better, simultaneously affect the original transparency of PC film hardly, because of but a kind of ideal PC film surface wettability control measures.Comparative example 3 adopts air plasma pre-treatment PC film surface, the preliminary adhesive power in the surface of film is improved greatly, for the preliminary attachment of hydrophilic material provides reliable guarantee, and then makes UV/O
3the object of process is uniform and stable, and the quality of modification PC film is promoted greatly.
In contrast table 1, embodiment 1 ~ 5 test result is visible, and along with the increase of mask hole area, the water droplet contact angle on PC film surface constantly reduces, and showing can its wettability of the surface of Effective Regulation by the patterning on PC film surface.As shown in Figure 5, wherein (d) ~ (h) is corresponding in turn to the PC membrane sample of embodiment 1 ~ 5 modification to concrete test result.
Comparative example 3,6,8,10,12, visible, when retaining hole area is identical, change dissimilar polarity type of polymer and mask hole shape, the water droplet contact angle on PC film surface is had a certain impact, but the final contact angle size variation on its surface is limited, the surface wettability of PC film therefore more effectively can be regulated and controled in conjunction with the design of mask hole area.
Claims (10)
1., by a method for patterned surface regulation and control Parylene C film surface wettability, comprise the following steps:
(1) Parylene C film, ultrasonic cleaning, dry;
(2) by the pre-treatment of above-mentioned Parylene C film air plasma;
(3) then, the polymeric coating of polar group is contained in Parylene C film surface-coated, dry;
(4) mask with patterning hole is placed in above Parylene C film, then at UV/O
3crosslinking reaction is carried out under effect;
(5) finally by the Parylene C film after crosslinked, the polymeric coating of wash-out removing unreacted grafting is soaked in deionized water, dry, obtain the film that patterning is modified.
2. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, it is characterized in that, in step (1), Parylene C film carries out ultrasonic cleaning in acetone and/or ethanol.
3. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, it is characterized in that, described in step (2), air plasma preconditioned voltage is 50 ~ 200V, and the treatment time is 1 ~ 60s.
4. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, it is characterized in that, the polymkeric substance containing polar group described in step (3) refers to the polymkeric substance being rich in hydroxyl, carboxyl, amino groups.
5. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, it is characterized in that, the described polar group polymkeric substance contained is one or more in polyacrylic acid, polyoxyethylene, Natvosol, chitosan quaternary ammonium salt, polyacrylamide.
6. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, it is characterized in that, the polymkeric substance of the described polar group contained is coated on Parylene C film surface with the solution form that mass concentration is 0.01 ~ 5%, and the solvent of solution is the one or both mixture in water, ethanol.
7. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, it is characterized in that, in step (3), coating method comprises the one in dip-coating, spin coating, spraying, brushing, roller coating.
8. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, is characterized in that, the hole of mask described in step (4) is the one in circular hole, tri-angle-holed, square hole, hexagonal hole.
9. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, it is characterized in that, the hole area of mask accounts for 5 ~ 50% of mask area.
10. the method by patterned surface regulation and control Parylene C film surface wettability according to claim 1, is characterized in that, UV/O described in step (4)
3treatment time is 10 ~ 600 seconds.
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